CN113318070A - Injectable hydrogel and preparation and application thereof - Google Patents
Injectable hydrogel and preparation and application thereof Download PDFInfo
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- CN113318070A CN113318070A CN202110570259.XA CN202110570259A CN113318070A CN 113318070 A CN113318070 A CN 113318070A CN 202110570259 A CN202110570259 A CN 202110570259A CN 113318070 A CN113318070 A CN 113318070A
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- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/06—Ointments; Bases therefor; Other semi-solid forms, e.g. creams, sticks, gels
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- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
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- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0057—Photodynamic therapy with a photosensitizer, i.e. agent able to produce reactive oxygen species upon exposure to light or radiation, e.g. UV or visible light; photocleavage of nucleic acids with an agent
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- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/0012—Galenical forms characterised by the site of application
- A61K9/0019—Injectable compositions; Intramuscular, intravenous, arterial, subcutaneous administration; Compositions to be administered through the skin in an invasive manner
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Abstract
The invention relates to an injectable hydrogel and preparation and application thereof, wherein the hydrogel is prepared by the following method: (1) adding an oxidant into the CNC solution, and performing modification treatment to obtain a modified CNC solution; (2) dissolving amino-containing organic micromolecules in an acidic solution to prepare a precursor solution, and performing hydrothermal reaction to obtain intermediate product carbon dots; (3) and adding the intermediate product carbon dots into the modified CNC solution, and performing ultrasonic treatment to obtain the target product. Compared with the prior art, the preparation method has the advantages that the CNC solution is used as the raw material, the amino-containing carbon points are used as the functional body, and the injectable hydrogel can be prepared by adding different contents and can be applied to tumor photothermal photodynamic therapy.
Description
Technical Field
The invention belongs to the technical field of preparation of gel materials, and relates to an injectable hydrogel, and preparation and application thereof.
Background
The rapid development of new materials and the high fusion of nanotechnology and biomedicine provide new opportunities for the development of new technologies for cancer treatment. The data of the world health organization shows that in 2020, 1000 million people die from cancer globally, and reports issued by the national cancer center show that about 1 million people in China have diagnosed cancer every day. The traditional tumor treatment means can kill cancer cells and kill normal cells by mistake, damage the immune system of the organism and even possibly cause secondary cancer of the organism. Therefore, there is a need to develop new therapeutic techniques to replace or combine the current therapeutic approaches to achieve effective treatment of cancer and improve the survival of cancer patients. In recent years, a nano platform based on multi-therapy cooperative treatment realizes the improvement of a single therapy and the treatment effect of more than two by the cooperation of functions of photo-thermal, photodynamic and the like of various nano materials, and is expected to bring a profound revolution to cancer treatment.
For example, chinese patent CN106074451A discloses a drug carrier containing carbon nanocages and its preparation method and application, which uses CNC as core and is coated with dendritic polymers, wherein the CNC surface, the polymers and the CNC and the polymers are all connected by disulfide bonds, the dendritic polymers are Polyamidoamine (PAMAM) with low generation numbers G0, G1, G2 and/or G3, and the PAMAM NH2 with amino terminal group or PAMAM COOH with carboxyl terminal group. The synthesis and preparation process of the carbon nanocages is complex and needs strict process control technology. In addition, as a carbon material, the carbon nanocages cannot generate a biocidal effect on cancer cells, have no direct tumor treatment effect, and need to carry external drugs to achieve the treatment purpose.
Disclosure of Invention
The invention aims to provide an injectable hydrogel and preparation and application thereof.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides a preparation method of injectable hydrogel, which comprises the following steps:
(1) adding an oxidant into the CNC solution, and performing modification treatment to obtain a modified CNC solution;
(2) dissolving amino-containing organic micromolecules in an acidic solution to prepare a precursor solution, and performing hydrothermal reaction to obtain intermediate product carbon dots;
(3) and adding the intermediate product carbon dots into the modified CNC solution, and performing ultrasonic treatment to obtain the target product.
Further, in the step (1), the oxidizing agent is one or a mixture of periodate, perchlorate and chromate. Optionally, in the step (1), the oxidizing agent is sodium chromate or sodium periodate.
Further, in the step (1), the addition amount of the CNC solution and the oxidant satisfies the following requirements: the mass ratio of the oxidant to the CNC is 1-6: 1, and can be selected to be 2-3: 1.
Further, in the step (1), the temperature of the modification treatment is 25-50 ℃, the treatment time is 1-10 hours, the pH is 2.5-7.0, and the preferred pH is 3.0-6.0.
Further, in the step (2), the amino-containing organic small molecule is an amine containing a benzene ring, and the amino-containing organic small molecule comprises at least one of aniline, o-phenylenediamine, m-phenylenediamine or p-phenylenediamine, and is optionally aniline.
Further, in the step (2), H in the acidic solution+The concentration is 1-3 mol/L.
Furthermore, in the step (2), the concentration of the amino-containing small organic molecules in the precursor solution is 1-10 g/L.
Further, in the step (2), the temperature of the hydrothermal reaction is 150-200 ℃ and the time is 6-20 h.
Further, in the step (3), the mass fraction of the modified CNC solution is 0.5-3%, optionally 1%, and the amount of the added intermediate product carbon dots is 2-10 g/L, optionally 5 g/L.
The second technical scheme of the invention provides an injectable hydrogel which is prepared by the preparation method, wherein the hydrogel is formed by crosslinking CNC (computerized numerical control) with amino-containing carbon points, and the surface of the CNC is modified by aldehyde groups.
The third technical scheme of the invention provides application of injectable hydrogel in preparation of a photothermal photodynamic therapy medicament.
The invention takes natural plant cellulose as raw material, and synthesizes CNC solution by acid hydrolysis, and because the CNC surface contains abundant hydroxyl, the invention is greatly beneficial to the modification of surface functional groups. And simultaneously, the amino-containing carbon dots with high light thermal efficiency and high light power effect are prepared. And crosslinking the CNC with surface aldehyde group modification and carbon points containing amino by using Schiff base reaction to prepare the hydrogel.
Compared with the prior art, the hydrogel can enrich nano-functional carbon dots in the hydrogel, and further enrich the carbon dots at the tumor part through the injectability of the gel, so that efficient tumor photothermal photodynamic therapy is realized.
Drawings
FIG. 1 is a scanning electron micrograph of a hydrogel obtained in example 1 of the present invention;
FIG. 2 is a SEM photograph of the hydrogel obtained in example 4 of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In each of the following examples, the hydrogel rheology was tested by an oscillatory shear rheometer for storage modulus and loss modulus in a frequency sweep mode at 1% strain. The linear strain of the hydrogel was measured in amplitude sweep mode at a fixed shear frequency of 1 Hz. And recording the temperature change of the hydrogel under the laser irradiation in real time through an infrared camera. The cancer cell killing effect of the hydrogel is detected by a CCK-8 experiment.
Otherwise, unless otherwise specified, all the conventional commercial raw materials or conventional processing techniques are used in the art.
Example 1
Step one, extracting a CNC solution from plant raw materials by using an acid hydrolysis method. Adding a certain mass of plant raw materials into a mixed solution of concentrated sulfuric acid and deionized water in a ratio of 1:1, heating and hydrolyzing at 65 ℃ for 1.5h, stopping heating, adding deionized water for dilution, standing overnight, removing supernatant, centrifugally cleaning, dialyzing, and performing ultrasound to obtain a CNC solution.
Step two, adding sodium chromate (the mass ratio of the sodium chromate to the CNC is 1:2) into the CNC solution, reacting for 5 hours at 35 ℃ with the pH value of 5, dialyzing, and performing ultrasonic treatment to obtain a surface modified CNC solution;
step three, preparing a carbon point precursor solution, wherein the concentration of aniline is 2g/L, and H of an acidic solution (prepared by adopting sulfuric acid)+The concentration is 1 mol/L;
and step four, taking the carbon point precursor solution obtained in the step three, taking 1/3 with the amount being the volume of the hydrothermal kettle, and carrying out hydrothermal reaction for 12 hours at the temperature of 200 ℃. And centrifuging, dialyzing and freeze-drying the hydrothermal product to obtain the carbon point.
And step five, taking the surface modified CNC solution obtained in the step two, adjusting the concentration of the surface modified CNC solution to be 1.5% (mass percent), taking 1mL, adding 4mg of carbon dots, and carrying out ultrasonic treatment for 5min to prepare the hydrogel.
Hydrogel concentration at 0.8W/cm2The temperature can be raised from room temperature to over 55 ℃ within 2min under the irradiation of 660nm laser, and the temperature meets the requirement of killing tumor cells. Meanwhile, carbon dots in the hydrogel can generate singlet oxygen, so that methyl orange is effectively degraded, and the hydrogel has an obvious photodynamic effect under illumination. Meanwhile, rheological tests show that when the strain of the hydrogel exceeds 23%, the loss modulus exceeds the storage modulus, and liquid fluidity is presented at the moment, so that the hydrogel has injectability.
Example 2
The specific method and steps are the same as example 1, except that: in step five, 2mg of carbon dots were added.
Example 3
The specific method and steps are the same as example 1, except that: in step five, 6mg of carbon dots were added.
Example 4
The specific method and steps are the same as example 1, except that: in step five, 8mg carbon dots were added.
Example 5
The specific method and steps are the same as example 1, except that: in the fifth step, the concentration of the surface modified CNC solution is adjusted to 1% (mass percent).
Example 6
The specific method and steps are the same as example 1, except that: in the fifth step, the concentration of the surface modification CNC solution is adjusted to be 2% (mass percent).
The results are shown in Table 1.
TABLE 1
The hydrogel is prepared by cross-linking CNC modified by surface aldehyde group and carbon points containing amino through Schiff base reaction. Rheological test analysis of the network cross-linked structure of the hydrogel indicates that the rheological properties of the hydrogel are related to the reactant content. In comparative example 1, when the CNC content of the surface aldehyde group modification was the same, the storage modulus and the loss modulus of the hydrogel increased with the increase in the carbon point content, which also indicates that the hydrogel network was formed from a higher crosslink density. FIGS. 1 and 2 are SEM images of the hydrogels of examples 1 and 4, respectively, and it can be seen that the pore size of the samples is significantly reduced, indicating a higher crosslink density between the components making up the hydrogel, consistent with the rheological results. Similarly, when the carbon dot content is the same, the storage modulus and the loss modulus of the hydrogel increase with the increase of the CNC content of the surface aldehyde group modification. When the strain is greater than 30%, the sample is pulled out of the linear strain region, where the loss modulus is higher than the storage modulus, and the hydrogel appears liquid-like, indicating that all samples remain injectable. The content of carbon dots affects the photothermal properties of the hydrogel in addition to the rheological properties. Along with the increase of the content of carbon points, the temperature rise rate of the hydrogel is obviously increased under the same illumination condition. On the contrary, the photo-thermal performance of the hydrogel is not obviously influenced by the change of the CNC content of the aldehyde group modification on the surface. In the absence of light, the hydrogels did not have significant killing effect on cells, showed good biocompatibility and negligible cytotoxicity. When light is applied, the hydrogel can generate photothermal and photodynamic effects simultaneously, cancer cells are greatly killed, and compared with the examples 1-4, the survival rate of the cancer cells is reduced along with the increase of the content of carbon points, so that the treatment effect is gradually enhanced.
Example 7
The specific method and steps are the same as example 1, except that: in the fourth step, the reaction temperature is 160 ℃ and the reaction time is 12 hours.
Example 8
The specific method and steps are the same as example 1, except that: in the fourth step, the reaction temperature is 180 ℃ and the reaction time is 12 hours.
Example 9
The specific method and steps are the same as example 1, except that: in the fourth step, the reaction temperature is 200 ℃ and the reaction time is 8 hours.
Example 10
The specific method and steps are the same as example 1, except that: in the fourth step, the reaction temperature is 200 ℃ and the reaction time is 4 hours.
The results are shown in Table 2.
TABLE 2
The hydrothermal reaction conditions have obvious influence on the photo-thermal efficiency and the photodynamic effect of the carbon dots. In comparative examples 7, 8 and 1, as the reaction temperature is increased and the reaction time is increased (examples 1, 9 and 10), the nucleation of carbon points is more complete, the photothermal conversion efficiency is improved, and the singlet oxygen generating capability of illumination is improved. This lifting effect is retained in the hydrogel. The change rule of the hydrogel temperature rise rate and the methyl orange degradation rate is consistent with the carbon point.
Example 11
The specific method and steps are the same as example 1, except that: in the second step, the reaction time is 1 h.
Example 12
The specific method and steps are the same as example 1, except that: in the second step, the reaction time is 3 h.
Example 13
The specific method and steps are the same as example 1, except that: in the second step, the reaction time is 7 h.
Example 14
The specific method and steps are the same as example 1, except that: in the second step, the reaction time is 9 h.
Example 15
The specific method and steps are the same as example 1, except that: in the second step, the reaction temperature was 25 ℃.
Example 16
The specific method and steps are the same as example 1, except that: in the second step, the reaction temperature was 40 ℃.
Example 17
The specific method and steps are the same as example 1, except that: in the second step, the reaction temperature is 45 DEG C
Example 18
The specific method and steps are the same as example 1, except that: in the second step, the reaction temperature is 50 DEG C
Example 19
The specific method and steps are the same as example 1, except that: in the third step, the concentration of the aniline is 1 g/L.
Example 20
The specific method and steps are the same as example 1, except that: in the third step, the concentration of the aniline is 4 g/L.
Example 21
The specific method and steps are the same as example 1, except that: in the third step, the concentration of the aniline is 6 g/L.
Example 22
The specific method and steps are the same as example 1, except that: in the third step, the concentration of the aniline is 8 g/L.
Example 23
The specific method and steps are the same as example 1, except that: in the third step, the concentration of the aniline is 10 g/L.
Example 24
The specific method and steps are the same as example 1, except that: laserThe power is 0.2W/cm2。
Example 25
The specific method and steps are the same as example 1, except that: the laser power is 0.4W/cm2。
Example 26
The specific method and steps are the same as example 1, except that: the laser power is 0.6W/cm2。
Example 27
The specific method and steps are the same as example 1, except that: the laser power is 1W/cm2。
Example 28
The specific method and steps are the same as example 1, except that: the oxidant used was changed to equal quality sodium periodate.
Example 29
The specific method and steps are the same as example 1, except that: the oxidant used was changed to equal quality sodium perchlorate.
Examples 30 to 32
The specific method and steps are the same as example 1, except that: the aniline is replaced by o-phenylenediamine, m-phenylenediamine or p-phenylenediamine respectively with equal mass.
Comparative example 1
Compared with example 1, most of them are the same except that the introduction of sodium chromate as an oxidizing agent is omitted.
The results show that without the use of an oxidizing agent, the CNC is not modified and does not form a hydrogel.
Comparative example 2
Compared to example 1, most of the same except that the aniline was changed to equal mass of benzene.
The results show that the synthesized carbon dots do not contain amino groups, cannot be cross-linked with CNC, and cannot form hydrogel.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A method of preparing an injectable hydrogel, comprising the steps of:
(1) adding an oxidant into the CNC solution, and performing modification treatment to obtain a modified CNC solution;
(2) dissolving amino-containing organic micromolecules in an acidic solution to prepare a precursor solution, and performing hydrothermal reaction to obtain intermediate product carbon dots;
(3) and adding the intermediate product carbon dots into the modified CNC solution, and performing ultrasonic treatment to obtain the target product.
2. The method for preparing an injectable hydrogel according to claim 1, wherein in the step (1), the oxidizing agent is one or more of periodate, perchlorate and chromate.
3. The method for preparing an injectable hydrogel according to claim 2, wherein in the step (1), the oxidizing agent is sodium chromate or sodium periodate.
4. The method for preparing an injectable hydrogel according to claim 1, wherein the CNC solution and the oxidant are added in an amount satisfying: the mass ratio of the oxidant to the CNC is 1-6: 1;
in the step (1), the temperature of modification treatment is 25-50 ℃, the treatment time is 1-10 h, and the pH is 2.5-7.0.
5. The method for preparing an injectable hydrogel according to claim 1, wherein in the step (2), the amino group-containing small organic molecule is an amine containing a benzene ring, and the amine comprises at least one of aniline, o-phenylenediamine, m-phenylenediamine or p-phenylenediamine.
6. The method for preparing an injectable hydrogel according to claim 1, wherein in the step (2), H is in an acidic solution+The concentration is 1-3 mol/L;
the concentration of the amino-containing organic micromolecules in the precursor solution is 1-10 g/L.
7. The method for preparing an injectable hydrogel according to claim 1, wherein the hydrothermal reaction is carried out at 150-200 ℃ for 6-20 h in step (2).
8. The method for preparing the injectable hydrogel according to claim 1, wherein in the step (3), the mass fraction of the modified CNC solution is 0.5-3%, and the amount of the added intermediate carbon dots is 2-10 g/L.
9. An injectable hydrogel prepared by the method of any one of claims 1 to 8, wherein the hydrogel is formed by crosslinking CNC modified with surface aldehyde groups with carbon points containing amino groups.
10. Use of an injectable hydrogel according to claim 9 for the preparation of a medicament for photothermal photodynamic therapy.
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Citations (4)
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|---|---|---|---|---|
| CN109180993A (en) * | 2018-07-16 | 2019-01-11 | 武汉理工大学 | A kind of preparation method of fluorescent nano-fiber element composite aerogel |
| KR20200051504A (en) * | 2018-11-05 | 2020-05-13 | 가톨릭대학교 산학협력단 | pH-sensitive carbon nanoparticles, a process for producing the same, and drug delivery using the same |
| WO2020172917A1 (en) * | 2019-02-28 | 2020-09-03 | 安徽大学 | Copper ion doped carbon dots, preparation and application thereof as photosensitizer for photodynamic therapy |
| CN112175209A (en) * | 2020-09-18 | 2021-01-05 | 苏州格睿光电科技有限公司 | Preparation method of carbon quantum dot modified nano-cellulose fluorescent hydrogel |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109180993A (en) * | 2018-07-16 | 2019-01-11 | 武汉理工大学 | A kind of preparation method of fluorescent nano-fiber element composite aerogel |
| KR20200051504A (en) * | 2018-11-05 | 2020-05-13 | 가톨릭대학교 산학협력단 | pH-sensitive carbon nanoparticles, a process for producing the same, and drug delivery using the same |
| WO2020172917A1 (en) * | 2019-02-28 | 2020-09-03 | 安徽大学 | Copper ion doped carbon dots, preparation and application thereof as photosensitizer for photodynamic therapy |
| CN112175209A (en) * | 2020-09-18 | 2021-01-05 | 苏州格睿光电科技有限公司 | Preparation method of carbon quantum dot modified nano-cellulose fluorescent hydrogel |
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